The Velociraptor! rock band also revealed their plan to perform their best-known hits during their prestige slot.
When asked by NME what songs they would play, frontman Tom Meighan replied: "All of them. The moment we walk on that stage, the place will come alive.
"That's where we're most comfortable. We love playing live rock 'n' roll. We thrive off it."
Meighan, who last graced the Reading stage in 2005, added: "We've not been to Reading and Leeds for a long time, we've done the Vs and the other places and it's nice to be asked back.
"They've been getting the same bands for the last five years, but it's an honour to play there."
The 'Fire' group are headlining alongside The Cure and Foo Fighters at the gig, taking place from August 24 to August 26.
> Check out the Reading and Leeds Festivals 2012 lineup in full
Watch Kasabian performing latest single 'Goodbye Kiss' below: